High-pressure crystal structure of elastically isotropic CaTiO3 perovskite under hydrostatic and non-hydrostatic conditions

The structural evolution of orthorhombic CaTiO3 perovskite has been studied using high-pressure single-crystal x-ray diffraction under hydrostatic conditions up to 8.1 GPa and under a non-hydrostatic stress field formed in a diamond anvil cell (DAC) up to 4.7 GPa. Under hydrostatic conditions, the TiO6 octahedra become more tilted and distorted with increasing pressure, similar to other 2:4 perovskites. Under non-hydrostatic conditions, the experiments do not show any apparent difference in the internal structural variation from hydrostatic conditions and no additional tilts and distortions in the TiO6 octahedra are observed, even though the lattice itself becomes distorted due to the non-hydrostatic stress. The similarity between the hydrostatic and non-hydrostatic cases can be ascribed to the fact that CaTiO3 perovskite is nearly elastically isotropic and, as a consequence, its deviatoric unit-cell volume strain produced by the non-hydrostatic stress is very small; in other words, the additional octahedral tilts relevant to the extra unit-cell volume associated with the deviatoric unit-cell volume strain may be totally neglected. This study further addresses the role that three factors--the elastic properties, the crystal orientation and the pressure medium--have on the structural evolution of an orthorhombic perovskite loaded in a DAC under non-hydrostatic conditions. The influence of these factors can be clearly visualized by plotting the three-dimensional distribution of the deviatoric unit-cell volume strain in relation to the cylindrical axis of the DAC and indicates that, if the elasticity of a perovskite is nearly isotropic as it is for CaTiO3, the other two factors become relatively insignificant.     

A hybrid pressure cell of pyrophyllite and magnesium oxide to extend the pressure range for large volume cubic presses

A hybrid pressure cell of pyrophyllite and magnesium oxide (HPCPM) used in large volume cubic presses is presented. In the HPCPM, a cubic frame which is made of pyrophyllite with face-centered square holes works as gaskets, and a heteromorphosis magnesium oxide works as the pressure-transmitting medium. Our experimental results indicated that the pressure-generation efficiency using the HPCPM was improved by about 40% than that using the traditional pyrophyllite pressure cell without decreasing the anvil truncation size (without sacrificing the sample volume). The HPCPM could pressurize samples of 1000 mm³ volume up to about 8 GPa, which is significantly higher than that available using the traditional pressure cell, which reports a highest pressure of about 6 GPa.     

一套基于六面顶高压装置的静水压高频介电测试系统

 以一套6×14 400 kN六面顶高压装置和一台Agilent 4294A精密阻抗分析仪为主体,建立了一套静水压高频介电实时测试系统。通过固体传压介质预成型方法,解决了液体测试腔在固体传压介质中的密封以及包括4根微同轴电缆在内的多根测量导线引出密封边问题,将常压下通用的四同轴阻抗谱测试技术引入了高压研究。液体测试腔容积可达(Φ13×15) mm³,可同时容纳10 mm×10 mm样品、高频测试夹具、温度与压力传感器、加热装置,以及包括4根外径为1.6 mm、特性阻抗为50 Ω微同轴电缆在内的16根引线,进行室温至300 ℃、常压至3 GPa 静水压力、测试频率40 Hz~5 MHz范围材料的四线阻抗谱测量,实验误差小于3%。利用这套装置观察了室温下,BaTiO₃单晶在约2.6 GPa静水压力下的压致铁电-顺电相变。     

六面顶压机立方压腔内压强的定量测量及受力分析

将六面顶压机立方压腔内置入电路,采用原位电阻测量确定Bi,Tl,Ba相变的方法,标定了压腔内不同位置的压力(强).通过标定立方压腔顶锤表面的压力并结合计算,分别得到了外部加载与压腔密封边受力以及合成腔体受力的对应关系.实验分析结果表明,随着外部加载的增加,当腔体压力达到5 GPa时,消耗在压腔密封边上的加载急剧上升,消耗在合成腔体的加载趋于不变,从而导致立方压腔压力达到上限.利用实验结果,分析了立方压腔在高压下的受力状态,解释了立方压腔的压力难以超过7 GPa的原因.结合立方压腔的几何结构,通过理论分析,提出了采用高体弹模量的物质作为传压介质,同时采用低体弹模量的物质作为密封边提高立方压腔压力上限的可行方案.通过定量标定叶腊石压腔轴向的压力梯度,给出了压腔内沿对称轴不同位置压力值的计算方法,此方法可为高压实验提供更精确的压力数据.     

Deviatoric stress: a nuisance or a gold mine?

Both synchrotron radiation and deviatoric stress were once considered to be nuisances. Now synchrotron radiation is one of the most important tools available to scientists of all disciplines and deviatoric stress is one of the most useful aspects of x-ray diffraction at extreme conditions. Samples in high-pressure devices are under true hydrostatic pressure only when surrounded by a fluid, thus limiting true hydrostatic pressure studies at ambient temperatures to pressures below about 11?GPa. Elevated temperature is able to extend this limit but has rarely been used for this purpose. Instead, noble gases have been used as pressure media as their solids are especially soft. Deviatoric stress and resultant anisotropic elastic strain in solid samples and solid media have led to many subtle errors in determinations of elastic properties and crystal structures, especially in the days before it was realized that they could be measured and were potentially a valuable source of information. In recent years, measuring anisotropic elastic strain by x-ray diffraction has provided new insights into materials strength, elastic properties, crystal structures, mechanisms of phase transitions, slip systems, lattice preferred orientation, and, of course, ways to make corrections when deviatoric stress is indeed a nuisance.     

Imaging of internal stress around a mineral inclusion in a sapphire crystal: application of micro‐Raman and photoluminescence spectroscopy

We developed a micro‐Raman and photoluminescence imaging technique for visualizing the internal stress fields in a sapphire crystal. The technique was applied to an Australian sapphire gemstone with a zircon inclusion. Considering piezospectroscopic effects on Raman and photoluminescence spectra, the Raman shifts of sapphire around the zircon inclusion were converted to hydrostatic pressure and deviatoric components of stress tensor. The internal stress was highly concentrated at the tips of the zircon crystal, where the deviatoric stress and the hydrostatic pressure component reached 700 and 470 MPa, respectively. Generation of compressive stress on the crystal surface of zircon can be explained by the difference in thermal expansion coefficients and elastic constants between sapphire and zircon. In general, internal stress fields induced by mineral inclusions reflect the pressure and temperature conditions at which the host sapphire gemstones were crystallized. Thus, the present technique can be utilized to identify the origin of gemstones. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of precompression on pressure-transmitting efficiency of pyrophyllite gaskets

Pyrophyllite is widely used both as a gasket material and as a pressure-transmitting medium, especially for a large-volume press. Its pressure-transmitting efficiency mainly depends on the following factors: geometry of anvil and pyrophyllite block, chemical composition, density and strength. For a long time, most studies have been devoted to the first two factors, whereas the third one has been studied less. In this work, we report that the pressure-transmitting efficiency of pyrophyllite is improved by precompressing. The results show that pyrophyllite was fully densified when the pressure reached about 1 GPa. The press load for Ba I–II transition in the cubic large-volume pressure cell is reduced more than 8×10⁵ N by using the densified pyrophyllite, compared with the unprecompressed pyrophyllite. Namely, the press-load utilization efficiency was improved above 15% when the precompressed pyrophyllite is used as a pressure-transmitting medium.     

Simultaneous determination of mean pressure and deviatoric stress based on numerical tensor analysis: a case study for polycrystalline x-ray diffraction of gold enclosed in a methanol-ethanol mixture

It is known that the {100} and {111} planes of cubic crystals subjected to uniaxial deviatoric stress conditions have strain responses that are free from the effect of lattice preferred orientation. By utilizing this special character, one can unambiguously and simultaneously determine the mean pressure and deviatoric stress from polycrystalline diffraction data of the cubic sample. Here we introduce a numerical tensor calculation method based on the generalized Hooke's law to simultaneously determine the hydrostatic component of the stress (mean pressure) and deviatoric stress in the sample. The feasibility of this method has been tested by examining the experimental data of the Au pressure marker enclosed in a diamond anvil cell using a pressure medium of methanol-ethanol mixture. The results demonstrated that the magnitude of the deviatoric stress is ～0.07?GPa at the mean pressure of 10.5?GPa, which is consistent with previous results of Au strength under high pressure. Our results also showed that even a small deviatoric stress (～0.07?GPa) could yield a ～0.3?GPa mean pressure error at ～10?GPa.     

Martensitic transformations in some ferrous and non-ferrous alloys under magnetic field and hydrostatic pressure

Martensitic transformations are extensively influenced by external fields, such as temperature and uniaxial stress, in transformation temperatures, crystallography and amount and morphology of the product martensites. Therefore, to clarify the effect of external fields on martensitic transformations it is very important to understand the essential problems of the transformation, such as thermodynamics, kinetics and the origin of the transformation, whose information is naturally useful in technological applications using the transformation. Magnetic field and hydrostatic pressure are important in such external fields because there exist some significant differences in magnetic moment and atomic volume between the parent and martensitic states. In the present paper, therefore, we summarizz the effects of magnetic field and hydrostatic pressure on martensitic transfonnations in some ferrous and non-ferrous alloys by referring to past and recent works made by our group and many other researchers. The transformation start temperatures of all the ferrous alloys examined increase with increasing magnetic field, but those of non-ferrous alloys, such as Ti-Ni and Cu-Al-Ni shape memory alloys, are not affected. On the other hand, the transformation start temperature decreases with increasing hydrostatic pressure in some ferrous alloys, but increases in Cu-Al-Ni alloys. The magnetic field and hydrostatic pressure dependencies of the martensitic start temperature are in good agreement with those calculated by our proposed equations.

During investigations of ferrous Fe-Ni-Co-Ti shape memory alloy, we found that a magnetoelastic martensitic transformation appears and, in addition, several martensite plates grow nearly parallel to the direction of the applied magnetic field in a specimen of Fe-Ni alloy single crystal.

We further found that the isothermal process in Fe-Ni-Mn alloy changes to athermal under a magnetic field and the athermal process changes to isothermal under hydrostatic pressure. Based on these facts, a phenomenological theory has been constructed, which unifies the two transformation processes.     

Finite-element analysis on pressure transfer mechanism in large-volume cubic press

Pressure transmission inside a large-volume cubic press was examined using finite-element (FE) simulations. Calculations were carried out for the pyrophyllite P-transmitting mediums (32.5?×?32.5?×?32.5?mm³). The cell pressures of the simulations were chosen as representative values, including 3.75 and 5.5?GPa. A modified constitutive model for pyrophyllite and more realistic modelling were proposed. The global pressure fields were displayed using the contour plots. The results reveal that (1) at the centre of the pyrophyllite cube exists a region of constant quasi-hydrostatic pressure (RoCQHyP) where the pressure drop is less than 50?MPa; (2) how mechanical property (e.g. bulk modulus) of the P-transmitting medium affects cubic press P-transmitting performance. The simulated results were corroborated by high pressure experiments.     

静水压加载单晶MgO的超声测量与压力标定

通过对单晶MgO的高压声速测量,结合高压Brillouin散射数据,对静水压加载条件下六面顶压机高压腔中的压力进行了多点系统标定(系统油压从15 MPa到51 MPa,间隔2 MPa),建立了新的大腔体压机超声测量和压力标定技术。相比传统的仅采用2~3个标定压力点的方法,该技术在统计上更加可靠。结合LY12铝的高压声速测量,进一步验证了该压力标定方法的合理性。与固体传压组装相比,固液混合传压组装在相同油压下的压力值系统偏低,分析认为这主要是由于固体传压介质中的剪切效应导致标定压力值系统偏高造成的。     

叶蜡石高温高压相变的荧光光谱研究

 对合成金刚石过程中，叶蜡石经高温高压淬火后的不同部位进行了研究。发现叶蜡石的两条荧光线14 428 cm^-1和14 398 cm^-1在高温和高压作用下均发生蓝移，温度压力共同作用比温度压力分别作用时两峰的蓝移明显减小。通过合成金刚石的温度、压力条件的共同作用，仅在靠近合成样品位置的叶蜡石发生了相变。本文认为造成蓝移的原因是温度压力的作用使电子能级或成键电子能级发生改变。     

高压腔内叶蜡石相变对发热石墨管电阻的影响

 在高温高压实验中，发现叶蜡石相变过程引起旁热式合成腔的加热石墨管电阻异常变化现象。对这一现象的若干规律及与叶蜡石相变的内在联系，进行了测试研究。本实验现象为在高温高压过程中实时地观察与研究叶蜡石相变规律，提供了可能性。     

A new hydrostatic medium for diamond anvil cells to 300 kbar pressure

We have shown that the rare gas xenon provides a hydrostatic medium for gasketed samples in a diamond anvil cell to pressures of 300 kbar. Previously, hydrostatic conditions were limited to ～100 kbar in a methanol-ethanol mixture. Three spectroscopic tests were used to determine that pressure gradients were small in the solidified gas. Since xenon has a convenient melting temperature, easy cell loading is possible. The small volume in the gasket requires only a few cm³ of gas. By analogy the other rare gases may be expected to show similar hydrostatic properties. Helium, for example, would be useful for X-ray studies.     

静态超高压大腔体中热流的计算机模拟(Ⅱ)计算结果与分析

计算了不同传压介质和加热筒变形对静态超高压腔中温度稳态分布的影响.稳态数值计算结果与近似解析公式结果及非稳态数值计算结果相符.由稳态最高加热温度对加热功率实验曲线斜率估算出叶蜡石的热导率与高压传热专门测量结果相符. 关键词：     

Hydrostatic pressure driven spin,volume and band gap collapses in SmFeO3: a GGA + U study

The crystal structure, magnetic and electronic properties of SmFeO₃ under hydrostatic pressure have been studied by first-principles calculations within the generalized gradient approximation plus Hubbard U (GGA + U). The iso-structural phase transition with spin, volume and band gap collapses can be induced by a large enough hydrostatic pressure. The high-spin (HS) state of Fe³⁺, with the magnetic moment of ~4 μ_B, is retained at low pressure. The spin crossover occurs at a transition pressure (~68 GPa) with the magnetic moment of Fe³⁺ decreasing to ~1 μ_B in low-spin (LS) state. Meanwhile, the reductions of cell volume (by ~?5.43%) and band gap (from >2 eV to ~1.6 eV) of SmFeO₃ are obtained when the HS–LS transition happens. Finally, the critical pressure of HS–LS transition, magnetic and electronic properties are found to be Hubbard U dependent.     

X‐ray reflectivity measurements of liquid/solid interfaces under high hydrostatic pressure conditions

A high‐pressure cell for in situ X‐ray reflectivity measurements of liquid/solid interfaces at hydrostatic pressures up to 500 MPa (5 kbar), a pressure regime that is particularly important for the study of protein unfolding, is presented. The original set‐up of this hydrostatic high‐pressure cell is discussed and its unique properties are demonstrated by the investigation of pressure‐induced adsorption of the protein lysozyme onto hydrophobic silicon wafers. The presented results emphasize the enormous potential of X‐ray reflectivity studies under high hydrostatic pressure conditions for the in situ investigation of adsorption phenomena in biological systems.     

Numerical simulation of multilayer stagger-split die and experiment on the bearing capacity

A high pressure device, multilayer stagger-split die, is investigated by finite-element analysis. We simulated the process of compressing pyrophyllite according to the Drucker–Prager criterion. Simulated results of both dies in the axial and radial directions are displayed and compared using the contour and path plots. We obtained the rate of pressure decay in the radial and axial directions, and analyzed the pressure distribution of the pressed pyrophyllite. The results demonstrate that in almost the same condition, the pressure of the multilayer stagger-split die is about 13.6% higher than that of the belt die, and the experimental result is higher.     

高压下TATB压缩性质的LDA和GGA比较研究

本文采用第一性原理密度泛函理论,结合平面波赝势方法,采用局域密度近似(LDA)和广义梯度近似(GGA)两种方法计算了TATB晶体在高压(0~7 GPa)压缩下的结构和物理性质,并与实验数据进行了比较.详细讨论了TATB晶体的晶体结构和分子构型随压力的变化.     

Mechanical properties of copper nanocube under three-axial tensile loadings

The mechanical properties of copper nanocubes by molecular dynamics are investigated in this paper.The [100],[110],[111] nanocubes are created,and their energies,yield stresses,hydrostatic stresses,Mises stresses,and the relationships between them and strain are analyzed.Some concepts of the microscopic damage mechanics are introduced,which are the basis of studying the damage mechanical properties by molecular dynamics.The [100] nanocube exhibits homogeneity and isotropy and achieves a balance easily.The [110] nanocube presents transverse isotropy.The [111] nanocube shows the complexity and anisotropy because the orientation sizes in three directions are different.The broken point occurs on a surface,but the other two do not.The [100] orientation model will be an ideal model for studying the microscopic damage theory.